Polymers containing units of carbon monoxide and one or more ethylenically unsaturated hydrocarbon are known in the art. Brubaker, U.S. Pat. No. 2,495,286, prepares such polymers of relatively low carbon monoxide content through the use of free radical catalysts, e.g., peroxy compounds. British Pat. No. 1,081,304 prepares polymers of higher carbon monoxide content in the presence of alkylphosphine complexes of palladium. Nozaki extended the scope of the reaction to include arylphosphine complexes of palladium halides, U.S. Pat. No. 3,694,412, and disclosed the use of unsaturated compounds other than hydrocarbons, e.g., vinyl acetate. A number of other references teach production of random copolymers or terpolymers of carbon monoxide and ethylenically unsaturated hdyrocarbons and non-hydrocarbons such as vinyl acetate or methyl acrylate. See, for example, U.S. Pat. No. 3,948,832. Published European application 0,121,965 published Oct. 10, 1984 teaches production of polymers in the presence of catalyst compositions formed from a palladium compound, an anion of a non-hydrohalogenic acid having a pKa less than 2 and bidentate phosphine ligands. Copending U.S. application, Ser. No. 935,431, filed Nov. 26, 1986, shows a similar catalyst composition incorporating bidentate nitrogen ligands.
When these references employ non-hydrocarbyl ethylenically unsaturated monomers in the production of polyketones, the unsaturated compounds have a functional group attached directly to a carbon atom of the ethylenic unsaturation through which the polymerization takes place, for example, vinyl acetate and methyl acrylate. Possible exceptions are shown by Nozaki, U.S. Pat. No. 3,835,123 and related patents where vinyl esters of unsaturated esters are listed as suitable monomers for the production of terpolymers with carbon monoxide and unsaturated hydrocarbon. The listed vinyl esters of unsaturated acids are vinyl crotonate and vinyl hexenoate. It is not exactly clear as to which of the unsaturated linkages serves as the site for polymerization, although the general teaching would suggest polymerization through the vinyl group rather than the unsaturation of the acid moiety.
Polymers of carbon monoxide and ethylenically unsaturated compounds, particularly when the polymers are linear alternating polymers of approximately equimolar quantities of carbon monoxide and unsaturate, are known as polyketones. These compounds contain carbonyl groups at regular intervals along the polymer chain. The polyketones have established utility as premium thermoplastics in a number of applications. Additionally, the properties of the polymers are modified by chemical reaction through the carbonyl groups. For example, catalytic reduction of the carbonyl groups followed by dehydration results in the presence of unsaturation in the polymer chain. Catalytic reduction in the presence of ammonia or hydrogen sulfide leads to the production of the polyamines or polythiols, respectively. This opportunity of modifying chemical structure and the resulting properties is an aspect of the utility of the polyketones. Other functional sites are provided by employing a functionally-substituted ethylenically unsaturated monomer as a component of the polymer chain. When an ethylenically unsubstituted compound having a functional group attached to a carbon atom of the ethylenic unsaturation is employed, the resulting polymer has other functional groups in addition to carbonyl attached to the polymer chain. For example, use of methyl acrylate as a comonomer results in the production of a polymer chain to which carbomethoxy groups are directly attached. Thus, use of ethylenically unsaturated compounds having various functional groups as a substituent on a carbon atom of the ethylenic unsaturation leads to polymers with a variety of functional groups attached to a carbon atom of the polymer chain. Such unsaturates are useful as components of terpolymers but on many occasions, copolymers with carbon monoxide are not easily produced and in some instances are not produced at all.
It would be of advantage to provide a process which employs functionally-substituted ethylenically unsaturated compounds wherein the functional group is not attached to a carbon atom of the ethylenic unsaturation. Use of such functionally-substituted ethylenic compounds permits the production of novel copolymers with carbon monoxide which contain functional groups not attached directly to the polymer chain as well as similar novel terpolymers which additionally contain moieties of ethylenically unsaturated hydrocarbon.